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Table of Content
05 May 2017, Volume 36 Issue 05
    Research progresses on production of light olefins from catalytic pyrolysis of biomass
    LUO Jun, SHAO Jing'ai, YANG Haiping, CHEN Yingquan, YANG Mingfa, CHEN Hanping
    2017, 36(05):  1555-1564.  doi:10.16085/j.issn.1000-6613.2017.05.001
    Abstract ( 447 )   PDF (534KB) ( 922 )  
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    With rapid increasing in dependence on foreign crude oil and aggravating in domestic conflict of supply and demand,there is a short of supply in stock of olefins,restricting the development of light olefins industry. Therefore,extending the kind of stock of light olefins and adopting non-petroleum stocks are very important. Using biomass as the stocks to produce light olefins is very promising. The process of catalytic pyrolysis production of light olefins is simple,overcoming the disadvantages,such as complex process and long production period,of traditional gasification process. But it is also affected by many factors,such as biomass properties,catalyst and pyrolysis process conditions. This paper mainly discussed the effects of categories of biomass,H/C effective ratio,AAEMS,temperature,ratio of catalyst to biomass,reactor,the methods of pyrolysis and the type of catalyst,on the yield of light olefins. Among them,the catalyst is the key factor of enhancing the yield of light olefins. At present,ZSM-5 is widely employed in the research of production of light olefins from catalytic pyrolysis of biomass,which is easy to deactivate due to carbon deposit. The modified catalysts have become the popular research subject. Two new methods of modifying catalysts are proposed. A conceptual design of new reactor was suggested,which may be useful for industrial applications.
    Research progress on development of phosgenation reaction technology in isocyanate industry
    BI Rongshan, HU Mingming, TAN Xinshun, ZHENG Shiqing
    2017, 36(05):  1565-1572.  doi:10.16085/j.issn.1000-6613.2017.05.002
    Abstract ( 377 )   PDF (486KB) ( 556 )  
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    Phosgenation reaction is the main technology to produce isocyanate in industrialization scale at present,which has advantages of mature process and high yields. However,there are still existing some potential hazards in safety and environmental protection because of phosgene and HCl as reactant and product in phosgenation reaction. This paper analyzed firstly the intrinsic defects of phosgenation reaction technology,combined with the phosgenation mechanism,and summarized the present states of improvements to the defects and concluded that two shortcomings of the technology can be solved step by step. Next,this paper retrospected the development history of phosgenation technology and summarized the internal mechanism of phosgenation progress based on reaction engineering,as well as presented the development tendency of phosgenation process. Finally,this paper briefly introduced some non-phosgenation technologies and agreed with that some of them will replace the present technology in the future but not in a short term while we compared the each features. Therefore,the further researches on phosgenation technology are necessary in promoting the technology of isocyanate industry and for the energy-saving and cost-reducing.
    Advance of alkylation process and concentrated sulfuric acid alkylation reactor
    LI Mingwei, LI Tao, REN Baozeng
    2017, 36(05):  1573-1580.  doi:10.16085/j.issn.1000-6613.2017.05.003
    Abstract ( 346 )   PDF (589KB) ( 626 )  
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    At present, the research of alkylation is mainly focused on the development of new catalysts and the strengthening of acid-hydrocarbon mixing process. The development of novel liquid acid alkylation reactors is one of the breakthrough points. In this paper, the status of alkylation technology at home and abroad were reviewed. The reaction process of solid acid,sulfuric acid,hydrofluoric acid and ionic liquid as catalyst were introduced. The mechanism of C4 alkylation was also reviewed. Based on the fact that the H- transfer of isobutane is the control step of the reaction, it was reported in this paper that the key of the development of alkylation is to strengthen the mass transfer of isobutane to acid phase, which is of great significance to the design of novel reactors. The reactors for concentrated sulfuric acid alkylation,which are divided into stirred mixing type, static mixing type, injection mixing type and shear mixing type according to the different ways of mixing,were emphatically introduced. This paper discusses several typical sulfuric acid alkylation reactors, including reactants mixing, products separation, and heat transfer. The advantages and disadvantages of various reactors are summarized,which is convenient for refiners to choose the reasonable alkylation reactor and process route.
    Evaluation of the node importance for large heat exchanger network based on complex network theory
    WANG Zheng, SUN Jincheng, LIU Xiaoqiang, JIANG Ying, JIA Xiaoping, WANG Fang
    2017, 36(05):  1581-1588.  doi:10.16085/j.issn.1000-6613.2017.05.004
    Abstract ( 260 )   PDF (599KB) ( 367 )  
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    Because of the complexity of large-scale heat exchanger network,it is important to investigate the importance of heat exchanger nodes in heat exchanger network. It can provide guidance for the control and safe operation of heat exchanger networks,as well as engineering practices. In this paper,the network topology structure of large-scale heat exchanger network was constructed by treating heat exchangers as nodes and treating the transfer of interference between heat exchangers as edges. Based on the complex network theory,the strategies and models for evaluating the node importance of the heat exchanger network were proposed. Firstly,the importance of nodes were evaluated by the multi-attribute decision method based on the degree centrality, betweenness,closeness and eigenvector centralities. Next,considering the direction of case heat exchanger network,PageRank algorithm was used to evaluate the importance of nodes. Considering the results from these two algorithms,the final results were obtained. The case analysis showed that the strategy is effective and it can evaluate the node importance from different views,which will enrich the node importance evaluation theory for heat exchanger network.
    Study on optimal multi-period operational strategy for steam power system in steel industry
    CHEN Jun, ZHOU Weiguo, WANG Hai
    2017, 36(05):  1589-1596.  doi:10.16085/j.issn.1000-6613.2017.05.005
    Abstract ( 225 )   PDF (447KB) ( 298 )  
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    Steam power steam including a variety of energy producers and demand over time, is an essential part of iron and steel companies. Factors of different equipment units, various sums of energy demand in each period, energy prices fluctuations with period and expense of changeover of each equipment unit between periods were taken into consideration respectively in this paper. A mixed integer nonlinear programming (MINLP) model was established, which is multi-period and steam-electricity coupled. The objective function is the sum of cost of energy in steam and power system during whole periods. The global optimal solution will be achieved by LINGO software, The core of which is mathematical programming. Based on the result and analysis of the calculation, it is demonstrated that initial operation condition has great influence on the result of multi-period optimization and LINGO solves this kind of model with high efficiency and reliability. It is analyzed that optimization result is to achieve the lower cost and high economic operation, which could be the basis of production and operation by the administrator.
    Planning optimization of PVC production by calcium carbide method based on discrete time representation
    WANG Yuhong, LIAN Xue, GAO Xiaoyong, FENG Zhenhui, HUANG Dexian, BAI Jianxun
    2017, 36(05):  1597-1604.  doi:10.16085/j.issn.1000-6613.2017.05.006
    Abstract ( 277 )   PDF (718KB) ( 244 )  
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    At present,polyvinyl chloride (PVC) by calcium carbide method had few studies in planning optimization. In order to solve this problem,a mixed integer nonlinear programming (MINLP) planning optimization model was established. A plant-wide process of PVC by calcium carbide method including raw material supply,calcium carbide production,salt water electrolysis,vinyl chloride (VCM) polymerization and the delivery of PVC was investigated in this paper. Considering the raw material cost,inventory cost,delay cost and electricity consumption cost,the working state and production rate of equipment,electricity supply and material supply were determined optimally based on the discrete time representation in order to minimize the total cost. According to the actual industry data,nonlinear electricity consumption characteristics of calcium carbide furnaces and electrolytic bathes were studied to reduce energy loss and improve the economic profits. A case study was provided to verify the effectiveness of the proposed model. The results showed that the proposed model is superior to the separate model in energy saving and total cost by 9.0% and 8.1% respectively.
    Purification of p-xylene by melt crystallization
    SHEN Shu, LI Shiyu
    2017, 36(05):  1605-1611.  doi:10.16085/j.issn.1000-6613.2017.05.007
    Abstract ( 319 )   PDF (2230KB) ( 524 )  
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    Adsorption separation of mixed xylene can obtain p-xylene,but it still contains a small amount of toluene. A new separation process of p-xylene and toluene by melt crystallization was proposed. The solid-liquid equilibrium phase diagram of p-xylene and toluene was measured by differential scanning calorimetry (DSC). The experimental data showed that the binary system presented a eutectic point. On the basis of the solid-liquid equilibrium,liquid film crystallization experiments were carried out. It can obtain p-xylene products with the purity over 99.5%. The results indicated that it was feasible to separate p-xylene and toluene by melt crystallization. According to the experimental process,the dynamic mathematical model of liquid film crystallization was established. The model values agreed well with the experimental data,which verified the accuracy of the model. With the model optimization of operating conditions,the appropriate spray density and cooling rate can weaken the problem of uneven crystal layer growth. Cost accounting about melt crystallization and distillation separation processes was carried out respectively. The results showed that the fixed investment of crystallization was much lower than the distillation and operation conditions were stable. Crystallization was easy to get high purity products,but its energy consumption was slightly higher than distillation. Thus,the crystallization was suitable for small batch production,and the distillation was appropriate for high-volume production.
    Analysis and optimization of distillation columns with feed splitting and preheating by considering a thermodynamic target
    LIU Xuegang, HE Chang, ZHANG Minkang, HE Changchun, LEI Yang, ZHANG Bingjian, CHEN Qinglin
    2017, 36(05):  1612-1618.  doi:10.16085/j.issn.1000-6613.2017.05.008
    Abstract ( 236 )   PDF (1203KB) ( 300 )  
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    The work systematically addresses an optimization approach of the energy-saving and hydraulic checking for distillation columns with feed splitting and preheating. To maximize the feed preheating efficiency (ratio of the reboiler duty reduction to the feed preheating duty),the key influencing parameters (e.g. amount of preheating,splitting fraction and feed locations) were adjusted by using invariant rectifying-stripping curves. Then,vapor-liquid distributing curve was employed to identify the tray with the lowest tray efficiency. Additionally,with the help of C++ programing and GUIDE tool in MATLAB,a professional hydraulic software,namely SYSU-DISTILL,with visualization window was developed. This software was used to analyze hydraulics of any tray with the lowest tray efficiency. A stabilization tower (it was assumed as an n-butane-n-hexane column) from the petroleum and chemical industry was used as an illustrative example. The thermodynamics results showed that an ideal feed preheating efficiency (100%) of this column can be reached when amount of preheating,splitting fraction and feed locations were 1000MJ/h,0.7 and 9/20,respectively. Meanwhile, the appropriate setting tray structure can achieve the goal of energy saving under guaranteeing normal operation of the distillation column from hydraulic checking. This work provided an insight into analysis and guidance in determining the optimal schemes for energy saving of actual distillation columns.
    Optimization of the process of nitrogen expansion refrigeration of BOG and the analysis of the adaptability of the sea
    CHANG Xueyu, ZHANG Yingying, ZHU Jianlu, LI Yuxing, ZHANG Mengxian, YANG Xiaoyu
    2017, 36(05):  1619-1627.  doi:10.16085/j.issn.1000-6613.2017.05.009
    Abstract ( 294 )   PDF (790KB) ( 592 )  
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    In the process of transportation of large LNG transport ship,it will absorb the heat from the outside world,and make LNG to be the natural gas. In order to avoid the risk of pressure overload of the LNG transport ship,it is a preferred treatment method to re-liquefy the nature gas using re-liquefaction system. In this paper,a new type of nitrogen expansion process was simulated and the key parameters of the process were optimized. By comparing the optimized process and propane precooled mixed refrigerant refrigeration process,the paper get some conclusions. First,the unit energy consumption of LNG was regarded as the measurement index. 5 key parameters (the outlet temperature of BOG gas in the heat exchanger,the outlet pressure of the BOG first stage compressor,the nitrogen outlet temperature of the heat exchanger,the pressure of the expansion of the expander and the pressure distribution of the nitrogen compressor) were optimized to reduce the power consumption of the system. Second,compared with the propane precooling mixed refrigeration process,the nitrogen expansion process has slightly higher unit energy consumption,simpler simulation,less equipment,smaller area and more secure. Third,the selected nitrogen expansion refrigeration process was more suitable for re-liquefying on LNG transport ship than propane precooled mixed refrigerant flow.
    Effect of multiple parameters on the anti-foaming performance and foaming control of formulated solvent UDS
    KE Yuan, SHEN Benxian, SUN Hui, ZHAO Yawei, ZHAN Guoxiong
    2017, 36(05):  1628-1634.  doi:10.16085/j.issn.1000-6613.2017.05.010
    Abstract ( 206 )   PDF (3629KB) ( 245 )  
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    Foaming control of alkanolamines is very important in high acid natural gas purification process. The effects of various parameters on anti-foaming performance of UDS solvent were studied. A semi-empirical foaming model was developed. The results indicated that the physical and chemical properties of UDS solvent,such as surface tension,viscosity and density,had significant impacts on anti-foaming performance of the solvent. The foaming model predicted the foaming performance of UDS solvent under different conditions very well. Four process parameters had distinct effect on the foam height. Specifically,the gas flow rate had the most effect,followed by CO2 loading,temperature and concentration of solvent. Surface properties of UDS solvent could be changed largely by impurities. Due to enrichment of impurity components in solvent,the physical and chemical properties of solvent became more sensitive to the acid components. The present studies are helpful of solving the potential foaming problems and helping operations in industrial purification plants.
    Experimental and CFD simulation on gas-liquid effective interfacial area in rotating zigzag bed
    ZHANG Bin, LI Yumin, GENG Kangsheng, JI Jianbing
    2017, 36(05):  1635-1641.  doi:10.16085/j.issn.1000-6613.2017.05.011
    Abstract ( 270 )   PDF (1334KB) ( 1146 )  
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    Gas-liquid effective interfacial area play a key role in rotating zigzag bed (RZB). The gas-liquid effective interfacial areas in a RZB were studied with chemical absorption of CO2 using NaOH solution in the mixed gases. The flow behavior of liquid in the rotor was simulated via CFD. The effects of rotor speed,gas flow and liquid flow on the effective specific surface area were studied. Experimental results showed that gas-liquid effective interfacial area in RZB is about 100-350m2/m3. Gas-liquid effective specific surface area increases with the increase of liquid and gas volume. It increases with the rotor speed slowly at first and than rapidly afterward. CFD simulation indicated that between the rotational baffle and stationary the droplet volume increased significantly and more static ring surface is covered by liquid membrane with the increase of fluid. Along with the increase of gas,the more liquid is broken into tiny droplets. Along with the increase of rotational speed,moving coil increases imposed on the centrifugal force and shear force of liquid. Liquid is better dispersed. Moving-coil droplet size becomes smaller. The values of ae of RZB rotor are lower than those of the multiliquid-inlet rotating packed bed (RPB),conventional RPB with stainless steel wire mesh,RPB with nickel foam packing and RPB with novel rotor of blades and multiple packing,and are close to the PRB equipped with blade packings and baffles.
    Improvement and experimental research on the performance of scroll expander using organic Rankine cycle(ORC)
    LI Lei, TAO Leren, SHEN Ling, HU Yongpan, LI Qingpu
    2017, 36(05):  1642-1648.  doi:10.16085/j.issn.1000-6613.2017.05.012
    Abstract ( 218 )   PDF (1323KB) ( 655 )  
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    The current efficiency of the organic Rankine cycle (ORC) is generally low.The performance of the expander has a direct impact on the cycle efficiency. In order to enhance the scroll expander performance of organic Rankine cycle,the scroll expander was improved. The movable scroll wraps do not block the inlet hole,the inlet and outlet are distributed symmetrically,and the scroll profile modification is adopted. The influence of inlet pressure,flow rate and rotating speed of the scroll expander on its performance was studied. The experimental results showed that the maximum external isentropic efficiency of the modified scroll expander would be up to 53%,and there is an optimal pressure value,which makes the maximum external isentropic efficiency of the expander. The increase of the inlet flow rate will increase the rotating speed and the output power of the expander. The changes of isentropic efficiency show parabolic curves,and different loads correspond to different optimal flow values,which makes the maximum external isentropic efficiency of the expander. Different loads of the expander have different optimal speeds,making the maximum output power,the optimal speed is larger as the inlet pressure increases. Research results showed that it is feasible to improve the scroll expander,and the experiments of expander point out the direction for further improvement.
    Influence of nanoparticles concentrations on pressure drop fluctuation of nano-refrigerant flow boiling in microchannels
    LUO Xiaoping, GUO Feng, XIE Mingyu, ZHANG Lin
    2017, 36(05):  1649-1657.  doi:10.16085/j.issn.1000-6613.2017.05.013
    Abstract ( 228 )   PDF (2383KB) ( 298 )  
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    Nano-refrigerants (0.1%-0.4% Al2O3/R141b) which used Span-80 as a dispersant were manufactured by ultrasonic vibration. They were used as working fluids to investigate the effect of nanoparticles concentrations on flow boiling pressure drop fluctuation under the designed conditions. An experiment on flow boiling of nano-refrigerant was conducted in rectangular microchannels with the hydraulic diameter of 1.33mm.The results showed that nanoparticles concentrations have significant impact on flow boiling pressure drop fluctuation of Al2O3/R141b. Under certain conditions,the average pressure drop of the 0.1%,0.2%,0.3%,0.4wt% nanofluids decreased by 9.4%,20.1%,23.2% and 36%,respectively,than the pure refrigerant,The standard deviation of the pressure drop was reduced on average 8.0%,22.7%,28.6% and 33.9%,accordingly. That indicates that total pressure drop decreases and the fluctuation is more gradual with the increase of nanoparticles concentrations. Scanning electron microscopy (SEM) and measuring surface static contact angle revealed that the deposition of nanoparticles on the surface of microchannels is more pronounced and the surface static contact angle become smaller with the increase of concentration. It proves that the cause of the influence of nanoparticles concentrations on flow boiling pressure drop and fluctuation is nano-refrigerant with higher concentration deposits more,reducing the roughness of the wall surface but increasing the wettability of the wall surface.
    A review of literatures on catalytic steam reforming of acetic acid for hydrogen production
    WANG Dongxu, XIAO Xianbin, LI Wenyan
    2017, 36(05):  1658-1665.  doi:10.16085/j.issn.1000-6613.2017.05.014
    Abstract ( 335 )   PDF (402KB) ( 556 )  
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    Hydrogen production via steam reforming of bio-oil,a potential way to produce hydrogen, can reduce environmental pollution and dependence on fossil fuels. Acetic acid is one of the main components of bio-oil and is often selected as a model compound. Nickel-based catalyst is widely used in the steam reforming of acetic acid,but it deactivates fast due to the carbon deposition. In this paper,the affecting factors for the steam reforming of acetic acid are analyzed. The coking mechanism of nickel-based catalyst in this process is illustrated. Optimization methods for nickel-baed catalyst are discussed,including optimizing the pretreatment process,adding promoters,and choosing appropriate catalyst supports. Research progresses in the thermodynamics analyses for steaming reforming of acetic acid are summarized. Further studies should be focused on the effects of a combination of a variety of promoters on carbon deposition. Catalytic activity and the synergy mechanism should be analyzed to produce a novel nickel-based catalyst with high activity,high resistance to caborn deposition for hydrogen production via steam reforming of bio-oil.
    The limited energy density and improving measurements for supercapacitors
    ZHANG Lei, HUANG Jun, ZHENG Junsheng, ZHENG Jianping
    2017, 36(05):  1666-1674.  doi:10.16085/j.issn.1000-6613.2017.05.015
    Abstract ( 230 )   PDF (1269KB) ( 440 )  
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    Supercapacitor is a new type of green energy storage device with high power density,long life cycle,and wide range of working temperatures. However,its energy density is quite low and is less than 1/10 of the advanced lithium ion batteries are. The low energy density of traditional supercapacitors is the main reason of their limted applications. For the traditional supercapacitor,the elements limiting the energy density include that:①only the surface materials of the electrode is used for the reaction;②the potential of electrode continuously changes during the charge and discharge processes;③the ions in the electrolyte get consumed during the charge process. As a result,reducing the consumption of ion in the electrolyte and improving the capacity of electrode become the effective measures to solve the problem of low energy density. And it includes the hybrid structure and lithium ion structure. Since the negative electrode can work as the source of lithium,lithium ion battery can choose much more different positive electrode materials and open the new gate for the researches.
    Research progresses on nanoparticle-stabilized foams in oil and gas production
    YANG Zhaozhong, ZHU Jingyi, LI Xiaogang, FEI Yang, XU Binyu
    2017, 36(05):  1675-1681.  doi:10.16085/j.issn.1000-6613.2017.05.016
    Abstract ( 281 )   PDF (657KB) ( 421 )  
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    Recently,as nanotechnology transforms traditional production methods,researchers have put forward nanoparticles for stabilizing foams aiming at improving the poor stability of foams. Similarities and differences between partially hydrophobic and hydrophilic nanoparticles for stabilizing foams were described and discussed in detail,which demonstrated that the main mechanism of stabilization is irreversible adsorption of nanoparticles at water-and-gas interface. The newest applications of nanoparticle-stabilized foams in the fields of enhancing oil recovery and foam fracturing fluids were summarized. Illustrating that nanoparticles can not only enhance stability of foams,but also improve the efficiency of foam fluids. However,the current problems of nanoparticle-stabilized foams are complicated interactions between nanoparticles and foams,high cost of modified nanoparticles,potential damage to the formation with low porosity and permeability and the lack of industrial applications. Future development directions were introduced such as reducing cost by using hydrophilic nanoparticles and surfactants together,concentration optimization of nanoparticles and surfactants according to different performance requirements of foams and applications to unconventional resources. Finally,the development potential of nanotechnology in oil industry was prospected.
    Simulation of oil shale pyrolysis using Aspen Plus user model
    BAI Jingru, LI Qifan, WU Haitao, BAI Zhang, WANG Qing
    2017, 36(05):  1682-1689.  doi:10.16085/j.issn.1000-6613.2017.05.017
    Abstract ( 306 )   PDF (627KB) ( 637 )  
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    It was used to build the oil shale pyrolysis model based on chemical structure,using Fortran language to compile mathematical model of the main components and embedding Aspen Plus based on user model.The main components of yield with the temperature change was simulated calculation.The accuracy of the results was verified by comparing document of the experimental data and simulation of the data.The results indicated that the simulation of the data for CO and CH4 agreed well with document of the experimental data.The analogue value of CO2 and shale oil had a good fit before about 600℃,while some deviations occurred after 600℃ due to the influence of decomposition of mineral substances.The simulation of the data for H2 in the beginning stages had a good fit with document of the experimental data,but the deviation degree slowly enlarged as time went on.Meanwhile,the yield of main components with time under different temperature was forecasted,It was found that the yield of main components first increased rapidly and then gradually stabilized at a constant value with the extension of time.When the temperature was relatively low,the yield of main components increased as time went by.When the pyrolysis temperature was further enhanced,the time required for organic matter decomposition was gradually reduced.The yield of the main component increased with the raise of pyrolysis temperature at the same time.
    Comparative study on the volumetric and gravimetric method for isothermal adsorption experiment of shale
    ZHOU Shangwen, LI Qi, XUE Huaqing, GUO Wei, LI Xiaobo, LU Bin
    2017, 36(05):  1690-1697.  doi:10.16085/j.issn.1000-6613.2017.05.018
    Abstract ( 281 )   PDF (588KB) ( 459 )  
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    Shale gas content is one key parameter to accurately evaluate the gas content and the resource potentiality of shale gas reservoir,and it is usually determined by isothermal adsorption experiments which mainly include volumetric method and gravimetric method. The volumetric method is commonly used in isothermal adsorption experiments,but the application of the gravimetric method is rarely. The adsorption capacities tested by volumetric and gravimetric method are excess adsorption,and the absolute adsorption can't be directly tested by experiments. And then the conversion relationship of the excess absorption and absolute adsorption is established. In order to compare the accuracy and stability of the two methods,the two isothermal adsorption experiments of same sample are performed respectively. The test results show that the adsorption curve is a type I adsorption curve at low pressure,but when the pressure is further increased,the isothermal adsorption curve will decrease. There is an inevitable downward trend of the isothermal adsorption curve at high pressure,which is not an abnormal phenomenon,but is the essential characteristic of excess adsorption capacity of supercritical methane. Comparative analysis show that the isothermal adsorption experiment based on the gravimetric method is less sensitive to experimental environment and parameters than the volumetric method. Especially for shale of lower adsorption capacity,the error caused by the volumetric method is greater than the gravimetric method. Under the existing technical level,the gravimetric method is more suitable for the isothermal adsorption experiment of shale.
    Research progress in the oxidative dehydrogenation of propane over vanadia-based catalyst: from aerobic to oxygen-free reaction
    CHEN Yanlong, ZHU Linhua, SI Tian
    2017, 36(05):  1698-1710.  doi:10.16085/j.issn.1000-6613.2017.05.019
    Abstract ( 346 )   PDF (2060KB) ( 345 )  
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    Oxidative dehydrogenation (ODH) of propane has become an attractive way to produce propene because of the low energy requirements for an exothermic and low temperature process,and little coke formation in the presence of oxygen. However,the low selectivity and yield toward propene are two main issues in propane ODH process over the past three decades which hinders its industrial application. In this paper,the possible mechanisms of ODH of propane over vanadia-based catalyst have been introduced in detail. The detrimental impact of O2 on the propene selectivity has been analyzed and the comparison of propane ODH with and without O2 has been carried out. New processes to improve propene selectivity and yield have been introduced. The applications of fluidized bed reactor and membrane reactor are discussed which might be a promising alternative for propene production in the future. The existence of O2 decreases the propene selectivity,and therefore,to realize ODH of propane in the absence of O2 and the catalyst regeneration at the same time will be a promising research direction.
    Advances in the noble metal-zeolite catalysts for aromatic conversion
    DENG Chenghao, QI Xiaolan, ZHENG Junlin, KONG Dejin, TANG Yi
    2017, 36(05):  1711-1718.  doi:10.16085/j.issn.1000-6613.2017.05.020
    Abstract ( 234 )   PDF (474KB) ( 447 )  
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    In this paper,recent advances on the aromatic conversion over metal-zeolite bifunctional catalysts have been reviewed. The synergistic behavior between metal and acid sites was discussed. Meanwhile,the dependences of catalytic performance on metal nature,properties of zeolites and pretreatment procedure were reviewed. By reviewing the reaction characteristics of the aromatic conversion over bifunctional catalyst,we pointed out that the introduction of metallic component into zeolites is an effective way to regulate the product distribution,improve the activity and stability of catalyst. Moreover,balancing between the metallic sites and acidic sites is the key to further optimize the catalytic performance,so as to inhibit the over-hydrogenation of aromatics and satisfy the requirements of activity,stability and product quality.
    Preparation and hydrogenation property of Ni-P amorphous alloy/acid-treated bentonite catalysts
    XU Yun, JIANG Yuexiu, QIN Zuzeng, JI Hongbing
    2017, 36(05):  1719-1726.  doi:10.16085/j.issn.1000-6613.2017.05.021
    Abstract ( 251 )   PDF (808KB) ( 385 )  
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    Catalytic hydrogenation of nitrobenzene to aniline is an important method for preparation of aniline,for which amorphous alloy catalysts exhibit rather high activity. The Ni-P amorphous alloy/acid treated bentonite catalysts were prepared by using an impregnation-chemical reduction method assisted by microwave-drying,and characterized by XRD,XPS,SEM,H2-TPR,and H2-TPD. The prepared catalysts were then used for the catalytic hydrogenation of nitrobenzene to aniline to study the relationship between the catalysts' structure and their performance. The results showed that the Ni-P amorphous alloy/acid treated bentonite prepared by the two methods were both of amorphous structure. Compared with the traditional drying method,microwave-assisted drying method increased the dispersion of the Ni active sites,changed their surface electronic state,and improved the interactions between Ni and the acid-treated bentonite. The catalytic activity and the stability of the Ni-P/acid-treated bentonite catalysts dried by the microwave-assisted drying method were significantly higher than those dried by the traditional drying method. When the nickel loading amount was 20%,and at 110℃ with an initial H2 pressure of 1.8MPa,the nitrobenzene conversion and the aniline selectivity over the Ni-P/acid treated bentonite amorphous alloy catalysts were 98.5% and 98.8%,respectively,which were still stable even after 6 recycles.
    Synthesis of hyperbranched nickel complex with isopropylamine as a core and its catalytic performance of ethylene oligomerization
    SHI Weiguang, FU Zijian, WANG Sihan, LIANG Hongjiao, HOU Shuang, LI Cuiqin, WANG Jun
    2017, 36(05):  1727-1733.  doi:10.16085/j.issn.1000-6613.2017.05.022
    Abstract ( 213 )   PDF (553KB) ( 292 )  
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    A novel 1.0G poly (amidoamine) hyperbranched molecule with isopropylamine as the core was synthesized,and its corresponding salicylaldimine nickel complex was synthesized by one-pot method with salicylaldehyde and nickel chloride hexahydrate. The intermediate and nickel complex were characterized by FTIR,1H NMR and ESI-MS. The optimal reaction conditions of this catalytic system were determined with methylaluminoxane as co-catalyst and toluene as solvent. The best conditions of oligomerization reaction were Al/Ni ratio of 1000,25℃,0.5MPa and 30min. Under these conditions,the catalytic activity was 3.8×105g Olig/(mol Ni·h),and the selectivity of olefin under C8 was as high as 99%. Through comparing the hyperbranched nickel complexes with different backbones,we preliminarily determined the influencing factors for hyperbranched nickel complexes in the oligomerization of ethylene.
    Carbon quantum dots: synthesis,properties and applications
    GAO Xue, SUN Jing, LIU Xiao, WANG Hua, HAN Jinyu
    2017, 36(05):  1734-1742.  doi:10.16085/j.issn.1000-6613.2017.05.023
    Abstract ( 503 )   PDF (4142KB) ( 1387 )  
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    As a kind of burgeoning carbon nanomaterials,carbon quantum dots have attracted much research attention in recent years,especially those prepared by using natural substances as the origin of carbon. In this review,various synthesis methods of carbon quantum dots were introduced based on the latest research progress,including top-down approach and bottom-up approach. In addition,we summarized the typical characterization methods for carbon dots,such as TEM,Raman spectrum,fluorescence spectrum,ultraviolet-visible spectrum,X-ray diffraction,and nuclear magnetic resonance. The properties of carbon quantum dots and their applications in bioimaging,biological sensing and detection as well as photocatalysis are also introduced. Finally,the future development of carbon quantum dots in photocatalysis and electrocatalysis are forecasted.
    Research progress on graphene in phase change materials
    ZOU Deqiu, MA Xianfeng, LIU Xiaoshi, GUO Jiangrong, HU Zhigang, WANG Binghui
    2017, 36(05):  1743-1754.  doi:10.16085/j.issn.1000-6613.2017.05.024
    Abstract ( 335 )   PDF (6422KB) ( 976 )  
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    Graphene has two-dimensional planar structure and excellent thermal conductivity. Adding it into phase change materials is a hot research topic all over the world. In this paper,the effect of graphene addition on the thermal properties of phase change materials was introduced,especially on the thermal conductivity,heat storage,heat transfer and phase change characteristics. The effect of graphene on the shape-stabilized performance of phase change materials was also analyzed,and the mechanism was revealed. Then,the effect of graphene on the encapsulation of phase change materials was discussed,and the performances of microcapsules with graphene as the wall additive and wall material were analyzed. Finally,the problems of preparation and properties on graphene composite phase change material were pointed out. The large-scale preparation of composite phase change materials,the mechanism of heat transfer and the synergistic enhancement of graphene and graphene oxide should be studied further in the future.
    Recent progress on TiO2-based composites for Li-ion battery anodes
    LI Junling, LI Tao, LI Weiwei, REN Baozeng
    2017, 36(05):  1755-1762.  doi:10.16085/j.issn.1000-6613.2017.05.025
    Abstract ( 268 )   PDF (409KB) ( 529 )  
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    As a kind of Li-ion battery anode materials,TiO2 is renowned for its high security. In order to compensate its low conductivity of electron and lithium,TiO2 material has been designed as a variety of nano structures and prepared into composites with materials with good electrical conductivity. In view of the recent research status of TiO2 based composite anode materials for Li-ion batteries,this paper has introduced some methods to prepare TiO2 based composite anode materials with carbon,silicon and metal materials. Moreover,advantages and disadvantages of these three kinds of materials were presented. Carbon materials are mature but they are flammable. Silicon materials possess high capacity,but their cycle performance is poor and the security is not good. Metal materials possess high electrical conductivity and are easy to alloy with other materials,but they are also poor in cycle performance. At last,it is proposed that the combining of carbon and TiO2 will be a promising way for industrial production of composite anode materials,and will be one of the most important research directions of Li-ion batteries.
    Preparation and application of porous materials by ice segregation induced self-assembly
    BU Yong, ZHANG Dongxiu, XIA Yongqing, WANG Shengjie
    2017, 36(05):  1763-1770.  doi:10.16085/j.issn.1000-6613.2017.05.026
    Abstract ( 265 )   PDF (2495KB) ( 479 )  
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    Macroporous and megaporous materials exhibit potential application in areas of catalysis,separation,energy,biomedicine and so on,because of their unique structures and properties. Up to now,many methods have been used to prepare such materials. Among them,ice segregation induced self-assembly (ISISA) has attracted great attention because of its unambiguous advantages in pore structure control and operation. In this review,we introduced the preparation mechanism,structure control,potential application,problems and outlook of porous materials by ISISA method. We focused on the regulation of the pore size,direction,morphology and wall thickness of the porous materials by changing the composition of the mixture or freezing conditions. Furthermore,we outlined that combination with other preparation methods and further functionalization of ISISA are two main development directions. This paper will be helpful for readers to understand the research status of ISISA and promote the application and development of porous materials.
    Research progress of CO2 adsorption using coordinatively unsaturated MOFs materials
    ZHAO Qian, FENG Dong, WANG Yang, ZHAO Wenbo
    2017, 36(05):  1771-1781.  doi:10.16085/j.issn.1000-6613.2017.05.027
    Abstract ( 314 )   PDF (4728KB) ( 559 )  
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    MOFs are a kind of potentially ideal adsorbents with coordinative unsaturated metal sites (UMSs). It can be used to separate and store small molecule gas. This article reviewed the development of MOFs materials in CO2 capture in recent years. We summarized some typical coordinatively unsaturated metal-organic materials,such as MIL series,Cu-BTC,MOF-74 and so on,which are suitable for capturing CO2. This work would help us to understand the metal-organic porous materials and expand their application in CO2 capture in the future. At the same time,this paper also pointed out that open metal sites play an important role on the adsorption performance of the porous MOFs materials. At present,the efficiency of porous MOFs materials for CO2 capture is far from the industrial requirement,so reasonable design of MOFs metal center,activating treatment after syntheses and the functionalized modifications on the pore channel surface would be the development directions for these type materials. At the end,we made the conclusions from the aspect of the preparation methods,the metal centers and surface modification.
    Progress of application for CO2 adsorption with phosphonate metal-organic frameworks
    NIU Zhaodong, GUAN Qingqing, CHEN Qiuling, NING Ping, GU Junjie
    2017, 36(05):  1782-1790.  doi:10.16085/j.issn.1000-6613.2017.05.028
    Abstract ( 247 )   PDF (1863KB) ( 308 )  
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    Phosphonate metal-organic framework (MOFs),one kind of the MOFs materials,has attracted much attention in recent years. In this work,the progress of phosphonate MOFs and its application in CO2 adsorption were reviewed. Moreover,the adsorption mechanism was expounded. The effects of crystallinity,effective specific surface area,porosity and water stability on the CO2 adsorption performance of phosphonate MOFs were discussed. In addition,the properties and characterization of new phosphonate MOFs containing N,N'-piperazinebis (methylenephosphonic acid) and its derivatives,phosphonate monoesters (PMEs) linkers were also reviewed. The effect of properties of piperazine ring,alkyl group,alkoxy group and hetero element (sulfur and fluorine) on CO2 adsorption performance of the phosphonate MOFs was summarized. The adjusting mechanism of the methyl,ethyl and alkoxy group on the pore structure of phosphonate MOFs were analyzed. However,the low specific surface area and porosity are still important restriction factors for the CO2 adsorption performance of phosphonate MOFs,while the core-shell structure of the MOFs material may give an effective solution.
    Preparation and functionalization of magnetic Fe3O4 nanoparticles and its application in heavy metal wastewater
    DUAN Zhengyang, LIU Shuli, XU Xiaojun, XIE Daolei, HE Changhua, WANG Yao
    2017, 36(05):  1791-1801.  doi:10.16085/j.issn.1000-6613.2017.05.029
    Abstract ( 296 )   PDF (760KB) ( 725 )  
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    As is known to all,with development of industrial and agricultural,heavy metals pollution as a toxic and harmful emission has seriously endangered the ecosystem and human health. Therefore,the research on the treatment of polluted wastewater becomes very urgent and meaningful. As a novel,highly efficient and renewable material,functional modified magnetic nanomaterials have been widely studied by researchers at home and abroad because of their remarkable effects on the purification of heavy metal wastewater in recent years. In this work,the traditional methods for the treatment of heavy metal polluted water are summarized and evaluated firstly. Secondly,the preparation methods of magnetic Fe3O4 nanoparticles are introduced,and the advantages and disadvantages of these methods are briefly discussed. Finally,the methods of amino-functionalization,carboxyl-functionalization and thiol-functionalization on the surface of magnetic Fe3O4 nanoparticles and their application in removing of heavy metal ions in aqueous solution are summarized. And the preparation,functionalization and application of magnetic Fe3O4 nanoparticles are prospected. We put forward that the preparation of magnetic Fe3O4 nanoparticles with controllable morphology,good dispersion and high stability and multifunctional magnetic Fe3O4 nanomaterials via improving and developing the surface functionalization process will be the main focuses of the research in the future.
    Modified oyster shell material and its PCBs adsorption characteristics
    FAN Liwei, ZHOU Hua, LU Zexiang, XIONG Lifeng, HAI Reti
    2017, 36(05):  1802-1810.  doi:10.16085/j.issn.1000-6613.2017.05.030
    Abstract ( 247 )   PDF (1184KB) ( 284 )  
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    With ferrous sulfate as the source of iron,the nano iron modified oyster shell material was prepared by the in-situ potassium borohydride reduction. The microstructure of the modified oyster shell material was characterized and its persistent organic adsorption performance of polychlorinated biphenyl (PCBs) was discussed. The experimental results showed that the particle size of nano iron in the modified oyster shell was uniform and had high degree of dispersion;the modified oyster shell material had excellent PCBs wastewater treatment performance. The PCBs adsorption rates of the modified oyster shell material could reach 96% and the adsorption amount is 2.97mg/g at the suitable reaction conditions:the solution temperature of 25℃,the initial PCBs concentration of 5mg/L,and the reaction time of 180min. These results clearly indicated that the modified material had good industrial application prospect as a low-cost and efficient adsorbent for treatment of persistent organic wastewater. Adsorption isotherm researches showed that the equilibrium data were found to follow the Langmuir adsorption isotherm closely. The adsorption was easy to implementand the increment of temperature was helpful to the adsorption. Analyzing from the point of the adsorption kinetics,the adsorption process conforms to pseudo-second-order equation (R2>0.99) ;the chemical adsorption was the main process; the adsorption rate was controlled by both the external diffusion and internal diffusion.
    Hydrothermal treatment and transesterification modification of rice straw for oil spill absorption material
    WANG Lei, LIU Changjian
    2017, 36(05):  1811-1817.  doi:10.16085/j.issn.1000-6613.2017.05.031
    Abstract ( 237 )   PDF (668KB) ( 345 )  
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    A biomaterial for oil spill adsorption was developed using hydrothermal treatment and transesterification modification of rice straw. Rice straw was pretreated by hydrothermal process to improve the fiber structure. Using vinyl acetate as esterification agent, N,N-dimethylformamide as solvent,and anhydrous potassium carbonate as catalyst for transesterification modification,the hydrophobic of the modified material was greatly improved. The process conditions of transesterification modification of hydrothermal treated rice straw were investigated. The optimum technological conditions were as follows: temperature 90℃,catalyst concentration 1.5g/mL,volume fraction of esterifying agent 20%,and reaction time 6h. The oil-absorption capacity and water-absorption capacity of the modified rice straw were 9.71g/g and 0.51g/g,respectively. Furthermore,the rice straw before and after modification were characterized by BET,XRD,and FTIR. The hydrothermally pretreated rice straw had larger pore diameters. The decrease of crystallinity and appearance of acetyl group of characteristic peak after transesterification showed the feasibility of transesterification modification of rice straw.
    Adsorption characteristic of moisture by precipitated silica including kinetics and thermodynamics analysis
    HU Zhibo, ZHENG Shuilin, CHEN Yang, LIU Yangyu, SUN Zhiming
    2017, 36(05):  1818-1824.  doi:10.16085/j.issn.1000-6613.2017.05.032
    Abstract ( 292 )   PDF (1100KB) ( 296 )  
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    Precipitated silica is an important adsorption material. The ability of moisture adsorption of precipitated silica was tested under different temperatures (15℃,20℃,25℃ and 30℃) and various relative humidities (RH=11%,33%,43%,75%,85% and 98%). And the dynamics of moisture adsorption was analyzed. The isothermal adsorption heat of precipitated silica was calculated based on the principle of thermodynamics of porous media isothermal adsorption. The adsorption mechanism was analyzed by XRD,SEM,FTIR,and pore structure. The results showed that the precipitated silica had excellent performance on the moisture adsorption. The moisture content reached 23.71% under the condition of 30℃ and 98%RH after 48 hours. Precipitated silica performed better under lower temperatures and higher relative humidities when the relative humidity was between 11% and 85%,while moisture adsorption ability increased with the rise of temperature when the relative humidity was 98%. The adsorption reaction was consistent with the pseudo second order kinetics equation. It could be concluded that the moisture adsorption isotherms is S type physical adsorption of condensable vapor in porous material,and Van der Waals force and hydrogen bond are the main forces.
    Preparation and characterization of double imine bridged mesoporous silica
    XIE Huilin, LONG Xiangnan, HU Wenbin, CHEN Xiuying, JIA Zhenyu, LIU Qihai, ZHOU Xinhua
    2017, 36(05):  1825-1830.  doi:10.16085/j.issn.1000-6613.2017.05.033
    Abstract ( 212 )   PDF (3141KB) ( 224 )  
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    Using self-made double imine silane coupling agent and ethyl silicate as silicon source,cetyl trimethyl ammonium bromide/sodium polyacrylate (CTAB/PAANa) as hybrid template agent,we synthesized double imine bridged functionalized mesoporous materials through copolycondensation method. And the structure of synthesized silicas were characterized by fourier transform infrared spectroscopy (FTIR),N2 adsorption-desorption,X-ray diffraction assay (XRD),scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Besides,the effects of dosage of sodium polyacrylate (PAANa) on its structure and morphology were emphatically investigated. The silicas were then applied in adsorption of heavy metal ions. The result showed that amount of PAANa had an effect on the specific surface area,pore volume and the degree of order of mesoporous materials. While the dosage of PAANa was 0.01%,mesoporous silicone (PMOS0.01) showed good morphology and degree of order. Moreover,under acidic condition,the adsorption capacity of Cr (Ⅵ) was 289.24mg/g,while that of Cu (Ⅱ) was 276mg/g under alkaline condition.
    Preparation and antibacterial activity of 1-hydroxy methyl-5,5- dimethylhydantoin/graphene oxide nanocomposites
    SONG Shaobo, ZHANG Hua, FU Haili, ZHANG Wen, LI Wei
    2017, 36(05):  1831-1837.  doi:10.16085/j.issn.1000-6613.2017.05.034
    Abstract ( 229 )   PDF (3633KB) ( 241 )  
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    By grafting modification of graphene oxide on the reaction,we prepared 1-hydroxy methyl-5,5-dimethylhydantoin/graphene oxide (1-MDMH/GO) nanomaterial. The structure and properties of 1-MDMH/GO was analyzed with Fourier transform infrared spectrophotometer,X-ray diffraction spectroscopy,X-ray photoelectron spectroscopy,scanning electron microscope and atomic force microscope. The antibacterial property of compound was separately tested using Staphylococcus aureus (S. cereus) and Escherichia coli (E. coli) as model system and analyzed by using bacteriostatic ring and plate count methods. The results showed that,1-hydroxy methyl-5,5-dimethylhydantoin was successfully grafted onto the graphene oxide (GO) and 1-MDMH/GO and GO were of single-layer nanosheet structure with large specific surface. The layer spacing of the composite was increased by 0.124nm compared with GO. After being contacted with the two bacteria for 24h,the bacteriostatic rate of the 1-MDMH/GO reached 97.9% for S. cereus and 92.4% for E. coli,which had enhanced by 25.0% and 33.3% respectively,compared with GO under the same condition.
    Preparation and properties of reduced graphene oxide/cellulose films
    WANG Dong, HUANG Yingwei
    2017, 36(05):  1838-1842.  doi:10.16085/j.issn.1000-6613.2017.05.035
    Abstract ( 230 )   PDF (1834KB) ( 459 )  
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    This study aims to use reduced graphene oxide (RGO) to improve the properties of cellulose (CE) in ionic liquid (IL) solvent. To achieve that,graphene oxide (GO) was dispersed in deionized water to prepare RGO using thermal reduction method,then the obtained RGO was mixed with IL. After removing the moisture by vacuum distillation,we obtained uniform dispersed reduced graphene oxide (RGO)/IL solution. RGO/IL was used as CE solvent and RGO was added to improve the property of CE film,the morphology of the materials were revealed using scanning electron microscope (SEM),and the structures were characterized with XRD. The results show that under the RGO loading of 1%,the tensile strength and modulus of RGO10/CE composite film was 122MPa and 6.77GPa respectively,which were 188% and 320% higher than that of CE film. The electrical conductivity of RGO/CE film was improved by 9 orders of magnitude,from 2.5×10-14S/m to 4.7×10-6S/m. It was due to the formation of new hydrogen bond between RGO and CE and the excellent two dimensional structures of RGO that made RGO significantly improve the thermal stability,mechanical properties and conductive capacity of the composite film.
    1,5-pentanediamine production by using Escherichia coli whole-cell biocatalysis lysine fermentation liquid
    QI Yanbin, MA Weicao, CHEN Kequan
    2017, 36(05):  1843-1847.  doi:10.16085/j.issn.1000-6613.2017.05.036
    Abstract ( 394 )   PDF (529KB) ( 398 )  
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    1,5-pentanediamine is a bioactive biogenic amine. L-lysine decarboxylase can catalyze with L-lysine to produce 1,5-pentanediamine. To reduce the production cost,whole cell catalytic production of 1,5-pentanediamine was outperformed using Escherichia coli AST1 and with lysine fermentation broth as the substrate. The effects of transformation pH,cell concentration,transformation temperature,PLP addition amount,and different kinds of acid on the transformation and the reusability of the cells were investigated. At the optimal condition,0.1mmol/L PLP,2.5g/L DCW and pH as 6.8,37℃,86.18g/L of 1,5-pentanediamine was obtained by transforming the fermentation broth containing 123.8 g/L L-lysine,and adjusting the pH using the acetic acid during conversion process. Furthermore,the cells can be reused five times and the substrate conversion rate maintained above 50% in the lysine fermentation broth. The reusability was better than that in the lysine solution,which greatly reduces the production cost and lays a foundation for 1,5-pentanediamine commercial production.
    Fabrication of electrostatic self-assembly chitosan hollow microcapsules and study of its loading and releasing properties
    OU Minhua, ZHANG Yongde, LUO Xuegang, ZHANG Siyue, QIAO Dan
    2017, 36(05):  1848-1854.  doi:10.16085/j.issn.1000-6613.2017.05.037
    Abstract ( 214 )   PDF (886KB) ( 436 )  
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    Chitosan hollow microcapsules,used as pesticide-loading carrier,were fabricated by self-assembly and sacrificial template method. Polystyrene,as the template,was first prepared through dispersion polymerization and sulfonated with H2SO4 afterward. Then the chitosan was employed to assembly onto the surface of sulfonated polystyrene electronically and cross linked it with glutaraldehyde so as to form the steady core-shell microspheres. Next,the tetrahydrofuran was applied to the removal of template and the cross-linked chitosan hollow microcapsules were successfully fabricated. To characterize the molecular weight,particle size and the size distribution of polystyrene microsphere,gel permeation chromatography and nano-particle size analyzer were used. Moreover,properties of the core-shell structure microspheres were confirmed by the zeta potentiometer,the scanning electron microscopy,the transmission electron microscopy,and the thermogravimetric analyzer. The model pesticide,imidacloprid,was then loaded on to the chitosan hollow microcapsule by way of passive absorption and permeation,and the release experiment was executed in methanol. Characteristic result from the fourier transform infrared spectrometer that was utilized to study the loading mechanism confirmed the hollow microcapsules interacted on imidacloprid with hydrogen bonding,which resulted in an extended releasing time. The result showed that the pesticide loading capacity of chitosan hollow microcapsules reached 31.78%. The initial burst release presented 56.63% of release rate. The loaded microcapsules maintained a certain amount of release,which demonstrated that the loading site of chitosan microcapsules was mainly on the surface and the pesticide staying inside the microcapsule wouldn't come out until the degradation of the microcapsules,which meant the loaded microcapsules had achieved the expected sustained-release effect.
    Application of analytical technology of LC-UV/MS fingerprint and chemometrics base on macamides in maca quality control
    SUN Xiaoqiang, HE Chuan, XU Defeng, YIN Yue, LI Zhengyi
    2017, 36(05):  1855-1861.  doi:10.16085/j.issn.1000-6613.2017.05.038
    Abstract ( 234 )   PDF (783KB) ( 236 )  
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    The liquid chromatography-mass spectrometric (LC-UV/MS) and standard chromatographic fingerprints of macamides in maca were established. Combined with chemometrics technology,the quality control of maca and maca-based products had been achieved using comparative analysis of components. Different regions of dried maca hypocotyls and dietary supplement tablets were used as samples,and the macamides were extracted by oscillations with petroleum ether. The extracts were analyzed using LC-MS,and the results indicated that a better separation of commom peaks was obtained in 40mins and nine of these peaks were identified as characteristic macamide peaks by mass data. The overall similarity among eight kinds of maca dried hypocotyls and dietary supplements was no less than 0.76,which indicated that varieties of macamides in all samples were similar. Principal component analysis was performed using the data of whole spectrum and characteristic peaks of macamides as input variables,respectively. The results indicated that using the data of characteristic peaks as input variables was the better choice for quality control of maca. All samples were divided into three categories on the basis of their real origins and types of samples; and three of nine characteristic peaks had greater effect on the quality control. This method has some merits such as stable,efficient and accurate,and it is suitable for the quality control and the origin identification of maca.
    Preparation of tea tree oil/urea formaldehyde-resin sustained release microcapsules
    GONG Sheng, CHEN Yan, HAN Wenqiang, ZHOU Xinhua, XU Hua, CHEN Huayao, WU Weichao
    2017, 36(05):  1862-1867.  doi:10.16085/j.issn.1000-6613.2017.05.039
    Abstract ( 246 )   PDF (2521KB) ( 446 )  
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    Using formaldehyde and urea as wall material of microcapsule and tea tree oil as core material,tea tree oil/urea formaldehyde resin microcapsules were prepared by in-situ polymerization so the adverse influence of volatile,oxidation and unpleasant smell could be avoided reasonably. In this study,the effects of the types of emulsifier,the amount of emulsifier,the curing time,the release of the environment, and other factors on the morphology,particle size,drug loading,and release properties of microcapsules were investigated. The results showed that,with the amount of 4% twelve sodium alkyl sulfate as emulsifier,the curing time about 80min,a good-shaped tea tree oil/urea formaldehyde resin microcapsule had been prepared with the most normal appearance,and uniform particle size,about 40-50μm,and compact wall. Furthermore,the tea tree oil loading and release performance was better. In this study,the microcapsule drug loading was up to about 45%,and 4 days release amount was about 68% under room temperature. Moreover,the duration of microcapsule release could be up to 7 days.
    Research progress on flue gas desulfurization and utilization with slurry
    TAO Lei, WANG Xueqian, NING Ping, LI Ziyan, WANG Langlang
    2017, 36(05):  1868-1879.  doi:10.16085/j.issn.1000-6613.2017.05.040
    Abstract ( 265 )   PDF (731KB) ( 667 )  
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    This paper summarized the applications of flue gas desulfurization and utilization withslurry. Applications of flue gas desulfurization and utilization about seven slurries including phosphate rock,pyrolusite,magnesium ore,red mud,zinc ore,copper mine and nickel ore were described, respectively. The quantities,occurrence forms of ores,flue gas desulfurization mechanisms,influencing factors,craft routes,operating parameters and application cases of desulfurization were discussed. Then advantages and disadvantages were compared and analyzed. It can be summarized that slurry prepared from the mixture of slag and water is used as a novel desulfurization agent for flue gas desulfurization,which could achieve the purpose of using waste to treat waste by realizing the removal of sulfur dioxide in flue gas and obtaining the comprehensive utilization of resources simultaneously. Analysis indicates that flue gas desulfurization with slurry has a feasible application prospect with low cost and large by-products,which could provide a promising new idea for flue gas desulfurization. However,there are still several problems such as less research on simultaneous treatment of many pollutants and high cost for separations of by-products. Therefore,it is important to strength subsequent researches on simultaneous treatment of many pollutants and separation and resource utilization of by-products in these fields.
    Membrane-based carbon dioxide separation from flue gases of coal-fired power plant-current status and developments
    SUN Yawei, XIE Meilian, LIU Qingling, MA Degang, JI Na, SONG Chunfeng
    2017, 36(05):  1880-1889.  doi:10.16085/j.issn.1000-6613.2017.05.041
    Abstract ( 301 )   PDF (1896KB) ( 546 )  
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    At present,the method of capturing CO2 in flue gas after combustion of coal fired power plant mainly includes chemical absorption,adsorption,membrane separation,low-temperature distillation. Chemical absorption is the most mature method,but the energy consumption of absorbent regeneration is higher,and there are some problems such as secondary pollution,equipment corrosion and so on. So it is very important to develop new technology with high efficiency and low energy consumption. This paper mainly reviewed the application of membrane separation technology in coal-fired power plant CO2 capture. The development in the membrane material design,optimization of membrane separation processes,and the influence of coexisting gaseous components and particles on the membrane separation CO2 in the flue gas of the coal fired boiler was summarized. At last,future trends of membrane technology has been put forward. Analysis showed that recent advances in the development of membrane materials and the optimization of membrane separation process have been rapidly developed. Therefore,membrane separation has shown a significant potential in high CO2 capture efficiency and low energy consumption. So the membrane separation has broad application prospects in the field of CO2 capture in the flue gas of coal-fired power plants.
    Application and research progress of ceramic membrane filtration technology in the treatment of oily wastewater in oil field
    HUANG Bin, ZHANG Wei, WANG Yingying, FU Cheng, XU Rui, SHI Zhenzhong
    2017, 36(05):  1890-1898.  doi:10.16085/j.issn.1000-6613.2017.05.042
    Abstract ( 280 )   PDF (1520KB) ( 397 )  
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    The treatment of oilfield oily wastewater is the key to the sustainable development of oil field. Ceramic membrane filtration technology has become a hot research topic due to its good separation effect and without secondary pollution. In this paper,the oil-water separation mechanism of ceramic membrane was analyzed,The research status of domestic and foreign ceramic membrane filtration treatment of oilfield oily wastewater was investigated. At the same time,application of ceramic membrane filtration technology in the treatment of oily wastewater in offshore oilfield was introduced. The influence factors on the effect of membrane filtration were analyzed,which are consist of the performance of the membrane itself,the nature of the raw material,the operating parameters of the process and so on. The performance of the membrane itself is mainly reflected in membrane pore size and membrane material. The nature of the feed liquid mainly depends on the oil content,pH,feed concentration and temperature. The operating parameters of the process mainly include trans-membrane pressure and membrane surface flow rate. Other factors mainly have reverse washing,adsorbent and coagulant. The fouling mechanism of membrane was analyzed,and the current cleaning method for membrane was introduced. Finally,the problems existing in the application of membrane technology were analyzed,and some suggestions for the future research has been put forward.
    Effects of coal combustion temperature on mercury emission and speciation
    WANG Chenping, DUAN Yufeng, ZHAO Shilin, LI Yaning, ZHU Chun, SHE Min, LIU Meng, WEI Hongqi, WANG Shuangqun
    2017, 36(05):  1899-1905.  doi:10.16085/j.issn.1000-6613.2017.05.043
    Abstract ( 275 )   PDF (914KB) ( 335 )  
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    The effects of different temperature on mercury speciation and transport during coal combustion were studied in a tube furnace device. EPA (Environmental Protection Agency) Method 26A and flue gas analyzer were used to determine the content of HCl/Cl2/NO/CO/O2/SO2 in flue gas. The change of flue gas components at different combustion temperature and the oxidation mechanism of Hg0 at flue gas cooling process were also investigated. The results indicated that mercury in coal was completely released and the discharge rate reached 97.9% at high combustion temperature (>750℃). Based on the analysis of oxygen,mercury began to release in coal combustion stage. The content of Hg0 became lower,while the content of Hg2+ was higher with increasing combustion temperature and close to 50% in flue gas at 900℃. Different temperature led to an obvious change in the flue gas components. The concentration of CO decreased gradually and the concentration of SO2 remained stable,while the concentration of NO/HCl/Cl2 became higher at elevated temperatures. NO/HCl/Cl2 can promote the oxidation of Hg0 at flue gas cooling process,but CO had the opposite effect. In addition,SO2 had unconspicuous effect on mercury speciation.
    Research on wet air oxidation of high-chloride chemical wastewaters and economic analysis
    LI Yanhui, WANG Shuzhong, SUN Panpan, YANG Chuang, WANG Laisheng, ZHANG Tuo, GUO Yang
    2017, 36(05):  1906-1913.  doi:10.16085/j.issn.1000-6613.2017.05.044
    Abstract ( 213 )   PDF (1913KB) ( 274 )  
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    High-chloride chemical wastewaters with higher organics concentration and strong causticity,is a great challenge in industrial wastewater treatment. We have investigated the effects of reaction temperatures,residence time,and catalyst Fe2+ content on TOC removal of the wastewater during wet air oxidation,and corrosion characteristics of candidate materials under atmospheres higher 20℃ than obtained optimal reaction temperature. On the basis of the above research,a comprehensive treatment process for this wastewater was also built. The results showed that a residence time of 60 min,a reaction temperature of 280℃,and catalyst Fe2+ amount of 100 mg/L was the optimum set of technological parameters for the degradation of the high-chloride chemical wastewater,under which the TOC removal rate was as high as 97.9%. For condition of 300℃,pH=13,nickel alloys (N10276 and N06625) suffered serious corrosion due to trans-passivation dissolution of alloying elements such as chromium and molybdenum in strong oxidizing & alkaline solutions,alkaline dissolution of solid nickel oxides or hydroxides,along with attacks of chloride ions against protective oxides film produced on alloys surface,while surface damage of titanium alloy TA10 also occurred,which mainly derived from strong alkalinity of environmental mediums (pH=13) causing chemical dissolution of the protective titanium oxides. If initial pH value of the corrosion media was adjusted to about 7.5,the corrosion rate of three alloys decreased obviously,and alloy TA10 showed satisfactory corrosion resistance. The economic analysis of wet air oxidation process for the high-chloride chemical wastewater with a capacity of 30 tons per day,indicated that the project total investment is 20.78 million Yuan,while the wastewater processing cost is 470.2 Yuan per ton.
    Dechlorinate effect of calcium-based waste during biomass combustion
    LI Shijie, HAN Kuihua, HAO Liyong, LU Chunmei
    2017, 36(05):  1914-1918.  doi:10.16085/j.issn.1000-6613.2017.05.045
    Abstract ( 239 )   PDF (427KB) ( 273 )  
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    Calcium-based sorbents are extensively used as an antichlor in most coal-fired power plants,which consume a large amount of calcium but have a poor dechlorination performance. In this study,the dechlorination performance of red mud,white mud,and acetylene sludge was explored on corn stalk,cotton stalk and rice straw. Air was used as experimental atmosphere,and combustion condition was simulated in a tube furnance. The experiment was carried out at temperatures of 400~900℃. The results showed that the dechlorination efficiency of white mud was 42.5% for rice straw,37.6% for cotton stalk. The dechlorination efficiency of red mud was 30.8% for corn stalk. But when the temperature was above 800℃,the dechlorination efficiency was getting lower with the temperature increase. Besides,different calcium-based wastes had different effects on different biomass materials. So suitable additives should be selected for combustions with different biomasses.
    Coordination of electro-osmosis and ammonium persulfate on sewage sludge deep-dewatering
    LI Yalin, LIU Lei, HOU Jinjin, LIU Xiaotong, HAN Ningning
    2017, 36(05):  1919-1926.  doi:10.16085/j.issn.1000-6613.2017.05.046
    Abstract ( 259 )   PDF (1590KB) ( 319 )  
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    Dewatered sewage sludge from sewage treatment plant was studied by self-made experimental reactor dewatering based on electro-osmotic-ammonium persulfate oxidation process which is influenced by the voltage gradient,mechanical pressure,dewatered sewage sludge thickness and persulfate dosage. Furthermore,response surface methodology has been applied according to the Box-Benhnken center-united experimental design principle to optimize parameters of electro-osmotic dewatering as a response index to indicate the reduction ratio of sludge water content. Meanwhile,the effect of constituent and distribution of extracellular polymeric substance on electroosmotic dewatering behavior of sludge was investigated. The results showed that the dewaterability can be improved by the combined of electro-osmosis-ammonium persulfate oxidation process. The combined effects of the dewatered sewage sludge thickness & voltage gradient and the sludge thickness & persulfate dosage are significant. The water content can be reduced to below 40% with voltage gradient of 24.97 V/cm,mechanical pressure of 35.95 kPa,persulfate dosage of 39.81 mg/g DS,sludge thickness of 2.35 cm. The protein content in extracellular polymeric substance is significantly correlated with the final water content of sludge after electro-osmotic- ammonium persulfate oxidation dewatering process.
    Pretreatment technology of desalination and deproteinization of corn cobs
    GUO Lei, YOU Weina, ZHAO Xin, HU Yangdong, WU Lianying
    2017, 36(05):  1927-1932.  doi:10.16085/j.issn.1000-6613.2017.05.047
    Abstract ( 243 )   PDF (1080KB) ( 251 )  
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    The exploitation and utilization of renewable biomass resources has now gained more momentum. The conditions of dilute-acid pretreatment of corn cobs were studied. The corn cobs were pretreated by water and dilute sulfuric acid (solid-liquid ratio 1g:10mL) at 80℃ and 100℃,and the process conditions were optimized. The analytical method of the metal ions removal rate from corn cobs extract was studied. The result shows that the content of metal ions in the extract can be expressed in the desalination rate of corn cobs. The removal rate of soluble protein in corn cobs in water at 100℃ is the highest. The sulfuric acid is not conducive to the removal of soluble protein; the high temperature and high acidity are beneficial for the removal of metal ions in corn cobs. The suitable pretreatment process for the removal of metal ions and soluble protein is that the corn cobs and deionized water first reacts for 0.5h at 100℃,then the corn cobs continue to react with the solution of 0.1% sulfuric acid for 1h. Using this pretreatment process,the removal rate of soluble protein and metal ions is 97% and 94.3%,respectively. The corn cobs pretreated had smooth and porous surfaces.
    Effect of CaO and sawdust on sticky properties of municipal sewage sludge during drying process
    DENG Wenyi, MEI Jing, LIU Yajun, YUAN Minhao, SU Yaxin
    2017, 36(05):  1933-1939.  doi:10.16085/j.issn.1000-6613.2017.05.048
    Abstract ( 208 )   PDF (874KB) ( 216 )  
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    The sticky properties of sewage sludge were tested using Jenike method and agitation method. The effects of CaO and sawdust on sticky properties were analysed. The results indicated that CaO can promote the adhesive and cohesive stresses of sewage sludge. In Jenike method,adhesive and cohesive stress increased by 58% and 28%,respectively when 5% (wet basis,WB) of CaO was added. Sawdust could markedly increase the cohesive stress,but it had no obvious effect on the adhesive stress. In agitation tests,lumpy phase of the sludge transferred to high moisture range by CaO addition. The moisture content in lumpy phase increased with the increase of CaO content in the examined 0-8%WB range. After 5%WB of sawdust addition,the range of lumpy phase increased markedly,so did the torque of dryer shaft. However,when sawdust content increased to 10%WB,the moisture content of the lumpy phase was increased,while the torque was decreased.
    Technology on preparing synthetic gas from industrial organic wastes by multicomponent slurry gasification
    LUO Jincheng, ZHANG Yong, GE Qiming, ZOU Tao, ZENG Mei, XIE Xinxin
    2017, 36(05):  1940-1945.  doi:10.16085/j.issn.1000-6613.2017.05.049
    Abstract ( 217 )   PDF (710KB) ( 226 )  
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    The organic waste is rich in hydrogen and carbon. It can be used as gasification raw material to produce synthetic raw gas with advantages of process cleaning and hydrocarbon recovery. There are many obstacles to overcome on converting organic waste to synthetic gas are needed,such as narrow range of organic waste gasification materials,difficulty of adapting to the large differences in the nature of organic waste,limiting gasification technologies in the field of organic waste treatment. According to different characteristics of the domestic industrial organic waste,animproved multicomponent slurry gasification (MCSG) technology for the organic waste is proposed in this paper. The basic principle of organic waste treatment was briefly discussed. Different treatment process route taken for different organic wastes and key equipment were introduced. Economy and technology for industrial applications were analyzed in this paper. The studies showed that the improved MCSG technology not only achieved the organic waste cleaning and reuse,but also had strong adaptability to the organic waste,and helped environmental protection,and provided economic benefits.
    Development and industrial production of THHC-I hydrocracking catalyst for producing light fraction
    XIAO Han, YU Haibin, ZHANG Jingcheng, ZHANG Yuting, NAN Jun, ZANG Jiazhong
    2017, 36(05):  1946-1952.  doi:10.16085/j.issn.1000-6613.2017.05.050
    Abstract ( 297 )   PDF (474KB) ( 235 )  
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    Regarding the prolific reforming raw material technology for the high nitrogen and naphthenic distillate hydrocracking,China National Offshore Oil Corporation (CNOOC) Tianjin Chemical Research & Design Institute Limited Corporation,by modifying the silica alumina ratio of the molecular sieves,the molecular sieves content of the supporter and the metal content of the catalysts,has successfully developed THHC-I hydrocracking catalyst,after pilot preparation,industrial amplification,and industrial production. The THHC-I hydrocracking catalysts for industrial production show the same physical-chemical properties and catalytic performance as the hydrocracking catalysts for pilot preparation and industrial amplification. The 1500h assessment results of the catalyst pilot test for Zhoushan coking heavy distillates show that the conversion of distillate with boiling point>345℃ is 75.8% and the liquid yield of naphtha with boiling point<170℃ is 42.7%. The sulfur and nitrogen content of naphtha are 1μg/g,0.6μg/g respectively. The sulfur and nitrogen content of diesel are 5μg/g,3μg/g respectively. The assessment results also indicate that THHC-I hydrocracking catalysts show excellent cracking activity,selectivity and stability. THHC-I catalyst has been accomplished 30 tons of production,and successfully applied in the coker heavy distillate hydrocracking using the prolific reforming raw material technology in CNOOC Zhoushan Petrochemical.
    Research on CO2 corrosion resistance performance of one kind environmental response cement stone
    PENG Zhigang, ZHANG Jian, ZOU Changjun, CHEN Dajun, ZHENG Yong
    2017, 36(05):  1953-1959.  doi:10.16085/j.issn.1000-6613.2017.05.051
    Abstract ( 209 )   PDF (5088KB) ( 381 )  
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    At present,the main materials for improving the CO2 resistance of cement mortar are active inorganic admixture,and the performance of which is limited,organic corrosion resistant materials are rarely reported. In order to improve the properties of cement's (ring) carbonation resistance,an environmental response type of cement stone was formed through adding an environmental response type of organic material. The changes of cement's compressive strength,permeability,pore structure and micro structure were studied at CO2 environmental maintenance condition. The results showed that the environmental response type cement effectively inhibited the increase of compressive strength and permeability through carbonization corrosion. The pore size of cement was refined. The harmful hole (>100nm) was decreased. The gel hole (<50nm) was increased and the total porosity was decreased by 16.31%. The phase composition of the hydration product remained stable,and the membranous substance which has a continuous distribution and close texture was formed in the corrosion surface. By using scanning electron microscope (SEM) analysis,it is revealed that the carbonation resistance mechanism was the membranous substance with dense mesh structure formed through rust preventer crosslinking,and the formation of hydration layer with thickness increasing on the surface of cement stone blocked the erosion channel and reduced the contact chance of the product with the corrosive medium. The purpose of enhancing the CO2 resistance of cement mortar was achieved. At the same time,it can be known by the SEM image of the cement with different adding amount of corrosion inhibitors that the quality of membranous substance may affect the ability of cement stone to resist the erosion of acid medium.
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